Method of making a high planarity, low CTE base for semiconductor reliability screening

ABSTRACT

The present invention relates to a system and method for performing reliability screening on semi-conductor wafers and particularly to a highly planar burn in apparatus and method for uses including wafer level burn-in (WLBI), diced die burn-in (DDBI), and packaged die burn-in (PDBI). The burn-in system includes a burn-in substrate with a planar base, a temporary Z-axis connecting member, and a Z-axis wafer level contact sheet electrically coupled to one another for screening wafers, diced die, and packaged electronic components, their assembly and use.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional of application Ser. No. 08/748,516,filed Nov. 8, 1996, now U.S. Pat. No. 5,830,565.

FIELD OF THE INVENTION

The present invention relates to a system and method for performingreliability screening on semi-conductor wafers and particularly to ahighly planar burn in apparatus and method for uses including waferlevel burn-in (WLBI), diced die burn-in (DDBI), and packaged die burn-in(PDBI). More specifically, a the present invention relates to a burn-insystem that includes a burn-in substrate with a planar base, a temporaryZ-axis connecting member, and a Z-axis wafer level contact sheetelectrically coupled to one another for screening wafers, diced die, andpackaged electronic components, their assembly and use.

BACKGROUND OF THE INVENTION

Semiconductor manufacturers who make integrated circuit chips begin bymanufacturing semiconductor wafers. Each wafer is typically 100 mm, 125mm, 150 mm, 200 mm or 300 mm in diameter and contains anywhere from oneto several thousand chips or die on the wafer. When manufacture of thewafer is completed, chips or die are cut or "diced" from the wafer andmay later be mounted into single chip or multiple chip packages forimplementation in a printed circuit board or other applications.

When manufacture of a wafer is completed, it is customary practice totest each chip on the wafer to determine whether each chip, asmanufactured, electrically matches design criteria, matches performancecriteria of the system in which the chip is to be implemented, and willbe reliable in operation. If a chip fails electrical testing orreliability testing, the chip is not suitable for implementation in asystem without repairing the chip or exercising redundancy featureswhich may have been designed into the chip. Performance testing of chipsmay be used to speed sort chips into different categories suitable fordifferent applications and sale at different prices.

Reliability testing is used to screen out chips having an undesirableshort life span. Typically, a significant percentage of a group of chipswill fail early in their lifetime due to marginal conditions duringmanufacture. Subsequently, a very low percentage of the group will failduring an extended period of use of the chips. Reliability screening ofsemiconductor chips is typically performed by a process of supplyingtest signal patterns to chips under test to repeatedly stimulate alldevices and wires on a chip, and is typically performed at elevatedtemperatures to simulate the first six months of operation. Therefore,the screening procedure is known as burn-in.

Burning in chips tends to induce accelerated failures. Two examples ofsuch failures are contamination induced failure at via interfaces, andgates and junctions, and in metal wires malformed during manufacturewhich may neck down to very thin regions on the order of 50% of thedesign width, which varies by technology and time but, is presently 0.35μm. The metal in these necked down regions will tend to drift in thedirection of electrical current flow by a mechanism known aselectromigration, where the rate of drift is directly proportional tocurrent density, accelerated by elevated temperature. Upon sufficientelectromigration, an open circuit condition will occur in the neckeddown region of the metal and cause a logical failure of the chip forsome test signal patterns. Gate oxide regions where transistors areformed using FET transistor technology are also a frequent source ofreliability failure. The thickness of a gate oxide region of atransistor must be controlled within exacting tolerances. If the gateoxide region of one or more transistors on a chip, as manufactured, istoo thin, the gate oxide may break down due to high electric fieldswithin the transistor when test patterns are applied to the chip. Uponfailure, output from the test patterns will evidence a failure.

While very valuable, the process of burn-in has historically been timeconsuming and expensive for semiconductor manufacturers. Existingburn-in is typically performed on integrated circuits at temperaturesbetween 90° C. to 125° C., for anywhere between 24 to 168 hours.Obviously, this slow rate of reliability testing impedes volumeproduction of functional semiconductors and adds tremendous cost.

Many manufacturers have attempted to address low throughput of knownburn-in processes by creating burn-in boards onto which many diced chipsare placed in chip packages, and then the packages go into sockets onthe burn-in boards. Thereafter, each chip on the test board issimultaneously exercised with test patterns at elevated temperatures.Thus, many chips are burned-in at once. These systems effectively reducethe time required to burn-in a large volume of chips. However, the addedcost of packaging defective or unreliable die is a significantshortcoming of such known burn-in processes.

Bare die burn-in (BDBI) is required to provide Known Good Die (KGD)determinations for multi-chip module's (MCM's) and other bare dieapplications, such as, chip-on-board (COB). Without bare die burn-in,yield of MCM's (and other bare die applications) is severely impaired,resulting in higher product costs. Current BDBI is typified by the TexasInstrument's "DIE MATE"® product where a bare die is placed into atemporary package and the burn-in test is performed. The requiredalignment and handling steps in this procedure add cost, processcomplexity, and time to provide bare dies that will be reliable or"Known Good."

Another technique for improving throughput of the burn-in process is toperform burn-in on whole or parts of whole wafers containing undicedintegrated circuits or chips. This process is known as wafer levelburn-in (WLBI). In wafer level burn-in, electrical terminals from a testapparatus are brought into intimate contact with contact pads of one ormore chips. It is therefore less destructive than soldering chips to aburn-in board. However, problems of planarity of electrical terminals ofthe test apparatus and with mismatch between the coefficient of thermalexpansion of the test apparatus and the wafer under test exist.

These problems have been addressed to date by several differenttechniques. For example, the industry uses a material known ascopper-invar-copper which is a high pressure, high temperature,lamination of copper on the outside of an interior INVAR sheet. One ofthe drawbacks with this material is that the maximum thickness it canobtain is in sheets that are 62 mils thick. A second drawback is thatwhen CIC is manufactured, it is rolled on a big spool. As a result,material from the outside of the spool to the inside of the spool has adifferent plastic deformation and hence radius of curvature.

Another drawback with the rolled CIC is that in order to get the desiredthickness and planarity, four pieces of CIC must be laminated together.There must be an even number of CIC layers because two layers may becurved down and one may be curved up. This results in an over balance inone direction or the other. So the number of CIC sheets must be anevennumber--2, 4 or 6. The drawback of using so many sheets of CIC isthat since CIC is very dense, the thicker the base, the heavier itbecomes.

Another disadvantage of the CIC system is that, as manufactured, thereis an individual piece of copper on both sides of the INVAR 36 goingthrough a lamination process through rollers. The thickness of thecopper top to bottom changes. As a result of the different thicknesses,stress differential warpage from top to bottom occurs, which is verydetrimental during thermal excursions. The thickness of the CIC couldchange as you go through the process also. You cannot machine down theCIC to a uniform thickness because you may machine off more on one sidethan the other.

Another disadvantage of the CIC system is that the material having thehighest coefficient of thermal expansion (CTE), the copper, is on theoutside. Thus, greater stress is generated with CIC.

One technique that is used to contact a wafer employs electricalterminals, such as S shaped probes or POGO® pins. With S shaped bendablewire probes, the test apparatus is brought into proximity of the wafer,and the S shaped probes are compressed back toward the test apparatus.The height of the test apparatus over the wafer can then be varied toensure contact between each of the S shaped probes and contact pads onchips of the wafer, despite a lack of planarity of the test apparatusand/or the wafer. However, the S shaped probes are difficult to align tothe contact pads of the chips on the wafer because they vary in X, Ydisplacement, as well as, in the Z direction on compression. Also, thenumber of pins used can be on the order of 20,000 to 40,000, or more,depending on the number of die per wafer and contacts per die, therebyincreasing the likelihood of non-alignment and mismatched pins.

POGO® pins suffer from shortcomings similar to the S-shaped probes.Although POGO® pins are compressible, therefore compensating for someplanarity differences between the burn-in substrate and the wafer undertest, POGO® pins present alignment challanges because the POGO® pinsmust be put into a fixture to hold them in place. The mechanical toolingcan have holes in slightly different locations due to normal tolerances.

Another technique for wafer level burn-in is described in U.S. Pat. No.5,541,524 to Tuckerman et al. There is disclosed a process of creating aburn-in substrate having metallic contact pads that are coined.Subsequently, solder is formed on the top of the coins. The solder topsare then brought into contact with the chip pads during burn-in testing.Here, the solder tops may not be substantially planar, and must deformupon contact with the chip pads. Thus, in order to achieve contactbetween all of the solder tops and the chip pads, compressive forcesmust be applied which may damage some portion of the chip pads.Furthermore, the solder tops must be periodically reworked by meltingthem back to a hemisphere to ensure integrity of burn-in. However, thiscan only be used to test wafers smaller than the apparatus. Currently,the system can only test 150 mm wafers if the apparatus is manufacturedon a 200 mm wafer, which does not provide a solution for testing 200 mmwafers.

Another technique for wafer level burn-in is described in U.S. Pat. No.4,968,931 to Littlebury et al. There, a flexible membrane probe, havinga plurality of contact pads, is compressed against a wafer havingintegrated circuits with mating chip pads. An inflatable bladder ispositioned behind the flexible member probe to bring the probe contactpads into contact with the chip contact pads. However, the bladder canonly compensate for gross irregularities in planarity. As the bladderinflates, the membrane is stretched moving the contact points. Thus,alignment is difficult. Also, only a limited number of traces can beimplemented to bring signals from the wafer to the test electronics,limiting the complexity of the system severely. In addition, the systemhas a high coefficient of thermal expansion, resulting in positionalvariation during thermal aging.

Thus, there exists a need to provide a wafer level burn-in device whichis highly planar and which is compliant, but at the same time maintainsthe structural integrity of the contacts of the device for contactingchip pads on a wafer. There is also a need for a burn-in system thateliminates the need for solder reflow or cleaning. There is also a needto provide a burn-in device having contacts, such as bumps, which areuniformly configured, precisely disposed, with a high degree ofstructural integrity for coupling the contacts of a wafer or the boardunder test. There further exists a need to provide a burn-in device witha base that has a low coefficient of thermal expansion matched to thewafer under test capable of successfully burning in large diameterwafers at elevated temperatures of up to 150° C., and as high as 200° C.

SUMMARY OF THE INVENTION

The present invention relates to a system and method for performingreliability screening on semi-conductor wafers that uses a highly planarburn-in apparatus. The burn-in apparatus includes a burn-in substrateunit with a high planarity base; a compliant, reusable, Z-axis memberunit which can optionally include an elastomer; and a reusable Z-axislaminated wafer level contact sheet unit.

The burn-in substrate and wafer level contact sheet are electricallycoupled to one another through the irregularly shaped conductive Z-axispathways that extend through the thickness of the compliant, Z-axismember that is sandwiched therebetween. The Z-axis pathways areelectrically isolated from one another in the X and Y axes directions.

A test signal from the burn-in substrate is conveyed to the componentbeing screened through bumps on the lower surface of the wafer levelcontact sheet that are registered and in contact with the componentbeing screened. Each bump at its upper end has a 4 to 8 mil pad andterminates in a tip that has a substantially planar configuration, and asurface diameter on the order of 0.25 mils and 2 mil (about 8 μm to 50μm), and preferably 0.5 mils to 2 mil (about 12 μm to 50 μm). Thus, thepad dimension to tip dimension ratio is between 2:1 to 32:1, preferablybetween 4:1 to 32:1.

The laminated wafer level contact sheet unit has an upper and lowersurface and includes a plurality of uniformly configured conductivebumps on its lower surface alignable with and corresponding to contactpads of an integrated circuit or other electronic component. Thegeometric configuration of the bump tip is sufficient to pierce an oxidelayer that is formed on the contact pad of the semiconductor component.The laminated contact sheet further includes a plurality of contact padson its upper surface, each individually electrically connected to acorresponding conductive bump through an open cell, porous layer havingselective Z-axis conductivity.

The base unit has balancing layers disposed on an upper portion thereofand circuitry layer on a lower portion thereof. The base unit includes adegree of planarity that is less than 0.01 inches per linear foot,preferably 0.001 inches per linear foot. The balancing layer may include"dummy" layers to off-set and balance the circuitry layers. A pluralityof first and second terminals form part of the circuitry layer, with thefirst terminals being coupled to a compliant, selectively conductive,Z-axis member, which may optionally contain an elastomer. The secondterminals are connectable to a test signal generator and the firstterminals.

The selectively Z-axis conductive compliant member is positioned betweenthe lower surface of the base unit and the upper surface of the waferlevel laminated contact sheet unit. The selectively conductive membercomprises a planar, open cell, porous material having an X, Y and Zaxis, with vertically defined cross-sectional areas electricallyisolated in the X and Y axis directions. The cross-sectional areasextend from one side of the material to another side and are coveredwith conductive metal, thereby being capable of electrically couplingthe first terminals to corresponding contact pads on the laminated waferlevel contact sheet unit.

The selectively conductive member of the present invention may containan elastomer in the porous material. When an elastomer is used incombination with the porous substrate, the temporary member is morereusable and less compliant than a Z-axis member lacking an elastomer.

Generally, the burn-in screening of electronic components includespositioning a burn-in unit in a temperature controlled environment, sothat downwardly depending conductive bumps can be coupled tocorresponding conductive pads of an electronic component to be screened.When the test signal is generated, it is conveyed through the burn-inunit to the conductive pads of the electronic component. The screeningis usually conducted at a temperature of at least 90° C., preferablybetween 125° C. and 200° C., for 8 to 168 hours, preferably between 8and 24 hours. The time of screening depends on th burn-in temperature,lower temperatures, longer burn-in time. Test signals are conveyed fromsaid the terminal to the first terminals, a first set of Z-axiscondcutive pathways, a second set of Z-axis conductive pathways throughconductive bumps.

More specifically, the present invention provides a system for burn-inscreening of electronic components, such as an integrated circuit or asemiconductor wafer, for example, where the wafer is contacted with aburn-in unit having a base member with a planarity of less than 0.01inches per linear foot and a coefficient of thermal expansion thatmatches the coefficient of thermal expansion of the wafer, +/-3 ppm. Thegenerated test signal is conveyed through the burn-in unit to conductivepads on a wafer.

The present invention also relates to a burn-in screening procedurewhere conductive bumps of a high planarity burn-in system are coupled toconductive pads of an electronic component. The bumps have tips betweenabout 10 μm to 50 μm in diameter.

Other objects, advantages and salient features of the invention willbecome apparent from the following detailed description, which taken inconjunction with the annexed drawings discloses the preferred, butnon-limiting, embodiment of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts a wafer having a plurality of integrated circuit chips.formed thereon, each chip including a pattern of contact pads forelectrical connection to the chip.

FIG. 2 depicts a burn-in device for wafer level burn-in with theconductive bumps of the laminated contact sheet raised prior tocontacting the wafer.

FIG. 3 depicts the burn-in device of FIG. 2 with the conductive bumps ofthe laminated contact sheet in intimate contact with the contact pads ofthe wafer.

FIG. 4 depicts an alternate embodiment of a burn-in device, in whichintimate contact between the laminated contact sheet and the wafer undertest is controlled by an inflatable bladder.

FIG. 5 depicts the base unit with upper balancing "dummy" layers andlower good "circuitry" layers according to the present invention.

FIG. 6 depicts a base unit having signal layers, a low CTE base layer,and five balancing layers.

FIG. 7 depicts a cross-sectional view of the pad layer showing contactpads and via holes through a dielectric layer.

FIG. 8 depicts a view of a signal layer illustrating signal traces on adielectric layer.

FIG. 9 depicts a cross-sectional view through the low CTE base layerillustrating its component layers.

FIGS. 10-12 schematically show the formation of irregular Z-axispathways extending through an open cell, porous substrate.

FIG. 13 depicts a porous substrate having isolated, Z-axis conductivepathways extending through the thickness of the substrate andterminating in conductive surface contacts.

FIG. 14 is a scanning electron micrograph of ePTFE material that is usedto prepare a Z-axis material which has a density of 0.22 gm/cm³, athickness of 76 μm and an air void volume of 70%.

FIG. 15 is a scanning electron micrograph of an ePTFE material that isused to prepare a Z-axis material which has a density of 0.40 gm/cm³, athickness of 40 μm and a 20% air void volume.

FIG. 16 is a scanning electron micrograph of an ePTFE material that isused to prepare a Z-axis material which has a density of 0.35 gm/cm³, aof thickness 100 μm and a 70% air void volume.

FIG. 17 is a scanning electron micrograph of an ePTFE material that isused to prepare a Z-axis material which has a density of 0.20 gm/cm³, athickness of 150 μm and an 70% air void volume.

FIG. 18 shows an 8 mil pad on a Z-axis material.

FIG. 19 shows an array of 8 mil pads with a 15 mil pitch on a Z-axismaterial.

FIGS. 20-34 depict the process sequence for forming the laminated waferlevel contact sheet of the present invention.

FIG. 35 is a scanning electron micrograph of a bump formed on the waferlevel contact sheet of the present invention.

FIG. 36 shows an enlarged view of the via and surrounding photoresistfor form a conductive bump on the wafer level contact sheet of thepresent invention.

FIG. 37 shows an isolated conductive bump and its dimensions.

FIG. 38 shows a scanning electron micrograph of an ePTFE material usedfor preparing an adhesive-filler composite.

DETAILED DESCRIPTION OF THE PRESENT INVENTION

The burn-in apparatus of the present invention includes: (1) a burn-insubstrate unit with a high planarity base; (2) a compliant, reusable,Z-axis member unit, optionally containing an elastomer; and (3) areusable, Z-axis laminated wafer level contact sheet unit, in a stackedarray, and its assembly. The burn-in substrate unit, which containscircuitry layers on a lower portion or surface thereof, and the waferlevel contact sheet are electrically coupled to one another when thecompliant, reusable, Z-axis member unit is positioned therebetween.

In FIG. 1 a semiconductor wafer 1 is shown having a plurality of chips2. The wafer 1 can be a silicon wafer or any other suitable materialsuch as, germanium, silicon germanium, silicon carbide, galliumarsenide, selenium, tellurium, InSb, BP, CdS, ZnSe, ZnTe, PbS, InP,PbSe, PbTe, InAs, GaSb, ZnS and Bi₂ Te₃. Each chip 2 on the wafer 1 hasa plurality of contact pads 3 that are brought into electrical contactwith the test apparatus to be described during testing. The chips 2 maybe memory chips such as, but not limited to, dynamic random accessmemories (DRAMS), application specific integrated circuits (ASICS),analog chips, or any combination thereof. Chips 2 are typically arrangedin columns 4, or rows 5 on the wafer so that upon completion of testing,the chips can be cut or "diced" from the wafer by sawing along thechannels. Subsequently, diced chips are used in applications bypackaging them in single chip modules (SCM), multi-chip module (MCM), ormounting them directly on a printed circuit board (COB).

The pretesting mode of the burn-in apparatus of the present invention isseen in FIG. 2. The burn-in apparatus 6 includes a base unit 7, acompliant, selectively conductive Z-axis member 8 which may contain anelastomer, a laminated wafer level contact sheet 9, a chuck 15 forreceiving a semiconductor wafer 1, and a test signal generator 10. Thebase unit 7 has a highly planar structure and is positioned above thewafer 1, and extends beyond the edge or edges of the wafer 1.

The base unit includes an upper surface 11 and a lower surface 12. Thelower surface 12 includes a plurality of first terminals 13 and secondterminals 14. The first terminals 13 and second terminals 14 areelectrically coupled together within the base unit 7.

The first terminals 13 are grouped in the center of the base unit 7,above the wafer 1 having a corresponding pattern to the pattern ofcontact pads of the chips 2 on the wafer 1. The second terminals 14 arealso on the lower surface 12 of the base unit 7, and are grouped outsideof the periphery of the first terminals 13. The second terminals 14 mayform a ring around the first terminals 13, may be grouped substantiallyon one side of the first terminals, or may be distributed over theentire lower surface 12 of the base unit 7 outside of the grouping ofthe first terminals 13. The second terminals 14 are connectable to thetest signal generator 10 at contacts.

A jig 16 encompasses the burn-in system and includes a mechanism 17 thatcan apply pressure to base 7 to engage Z-axis material 8 and contactsheet 9 to have the bumps 18 thereon engage the pads of the wafer 1. Thebumps are best seen in FIGS. 34 and 35.

As shown schematically in FIG. 3, the connection between terminals 14and generator 10 may be accomplished by raised members terminating in aplurality of compressible pins 14, such as POGO® pins or S shaped pins,on an upper surface 20. The compressible pins 21 are electricallycoupled through the raised members to the test signal generator 10 andare arranged in a mating pattern to the pattern of second terminals 14on the base unit 7.

The laminated wafer level contact sheet 9 of the present invention maybe substantially the same size as the wafer 1 and has contact pads 20arranged in a pattern corresponding to the first terminals 13 and thecontact pads 3 on the wafer 1. The terminals 13 are contact pads whichare formed from at least one metal layer, such as copper, nickel, gold,platinum, palladium or cobalt, with a layer thickness of between 1 μmand 50 μm, and dimensions of between 25 μm×25 μm and 250 μm×250 μm, andany desired shape.

The contact pads 20 on the surface of the laminated wafer level contactsheet 9 are aligned to the first terminals 13 on the base unit 7 and aretemporarily attached to the lower surface of the base unit by theselectively conductive member 8. The selectively conductive member 8provides electrical contact between the first terminals 13 of the baseunit 7 and the contact pads 20 on the laminated wafer level contactsheet 9.

The wafer level contact sheet 9 also has raised bumps 18 on a lowersurface thereof that terminate in a tip having a diameter of 0.25 to 2.0mils. The raised bumps 18, best seen is FIGS. 34 and 35, are identifiedas reference numeral 67. The raised bumps 18 have a patterncorresponding to the contact pads 3 on the wafer 1 and are individuallyelectrically coupled to the contact pads 20 on the upper surface of thelaminated wafer level contact sheet 9, best seen in FIG. 34.

When a wafer 1 is place on the chuck 15, the wafer 1 is aligned so thatthe pattern of contact pads 3 on the wafer 1 corresponds to the patternof raised bumps 18 on the laminated wafer level contact sheet 9.Alignment may be accomplished by any of several techniques, includingoptical alignment, infrared alignment, x-ray alignment, or mechanicalalignment, such as, using pits formed on the wafer level contact sheet 9which mate to protrusions on the wafer 1 (not shown). The wafer 1 may beheld to the chuck 15 by a mechanical jig 16 and 17, by creating a vacuum(not shown) between the wafer 1 and the chuck 15, or by mechanicalcoupling.

FIG. 3 depicts the burn-in apparatus of FIG. 2, wherein the raised bumps18 of the laminated wafer level contact sheet 9 have been brought intointimate contact with the contact pads 3 of the wafer 1. Also, thesecond terminals 14 on the base unit 7 have been brought into contactwith the compressible pins 21 on the test signal generator 10.Alternatively, contact may be made by a piston which pushes the raisedbumps of the burn-in device against the contact pads 3 of the wafer 1and the second terminals 14 against the compressible pins 21 of the testsignal generator 10. Contact may be accomplished by creating a vacuumbetween the raised member of the test signal generator and the baseunit.

A heating element (not shown) may be included within the chuck 15 forsupplying heat to the wafer 1 in order to elevate the temperature ofintegrated circuits on the chips 2 under test to a desired burn-intemperature. In cases of high-power chips on the wafer, heat produced bythe chips 2 under test may elevate the temperature of the integratedcircuits above the desired burn-in temperature. In such a case, thewafer may be cooled by blowing cold air over the wafer, by including acooling element in the chuck 15, or by many other known techniques.Alternatively, the entire jig may be located within a temperaturecontrolled environment to provide the elevated temperatures for theburn-in procedures. Techniques for controlling temperature insemiconductor manufacturing and testing are well known.

FIG. 4 depicts an alternate embodiment of the invention, whereincompressive force applied to the burn-in device 6 is supplied by aninflatable bladder 24 having a source of fluid (not shown) through valveconduit 25. Inflation may be accomplished with liquid or a gas, and maytend to compensate for any tilting of the burn-in device relative to thewafer under test.

In an alternate embodiment of the invention, the test signal generator10 may be coupled to the second terminals 14 by a variety of techniques,including by a rigid connector or flexible conductive tape. The secondterminals 14 may be located on the surface 12 of the burn-in device,arranged in a pattern substantially contained within the area of thewafer 1 below. In this scenario, the burn-in device 6 itself might be nogreater in size than the wafer itself.

BASE UNIT:

The base unit is best seen in FIG. 5 and includes a high planarity base25 formed from low coefficient of thermal expansion (CTE) material orhaving a matched composite CTE obtained through laminated layers of lowand high CTE material. The base unit includes a stack of good circuitrylayers 26, each layer includes a metal layer and a dielectric layer.Layer 27 of the base unit 7 includes dummy layers 27 which are used tobalance circuitry layers 26. The lower surface 28 includes the first andsecond terminals 13 and 14.

FIG. 6 depicts a base unit of the present invention which includes goodcircuitry layers 32, a low CTE base 31 or base 31 having a low compositeCTE or matched CTE, and balancing layers 30. The base unit 29 has a padlayer 33, three signal layers 34, 36 and 37, a core layer 35, a low CTEbase layer 31, and balancing layers 30. Layers 33-37 form the "good"circuitry layers 26 of base unit 29. Having three signal layers, 34, 36and 37 facilitates routing a large number of signals between the firstand second terminals 13 and 14 of the base unit 29. Positioning the corelayer 35 between signal layers provides predictable impedance for signaltraces on each of the signal layers 34, 36, 37 and reduces electricalnoise within the base unit 29. The low-CTE base 31 constrains thermalexpansion of the base unit 29 and contributes to maintaining highplanarity of the base unit 29. Although the good layers 33-37 andbalancing layer 30 have 5 layers, more or less layers are possible.

The balancing layers 30 are preferably as numerous as the number of"good" circuitry layers 26. The balancing layers should match the copperand dielectric density of the corresponding layers within the "good"circuitry layers 26 on the opposite side of the low-CTE base 31.Matching the density on opposing sides of the low CTE base 31 helpsmaintain the planarity of the base unit 29.

The balancing layers 30 may not contribute at all to the electricalperformance of the base unit 29 and may be used entirely to maintain theplanarity of the base unit 29. Therefore, the balancing layers 30 may beimplemented with signal layers and core layers that have been scrappeddue to manufacturing defects but which have a substantially similardensity to corresponding "good" signal layers 34, 36, 37 and core layers35 on the opposite side of the low-CTE base. However, the balancinglayers could be additional "good" circuitization layers.

The core layer 35 is formed with a continuous sheet of conductivematerial laminated to a dielectric layer. The conductive material can behalf-ounce copper, or one ounce copper. In place of copper, any metalhaving a high CTE could be used, such as, but not limited to, stainlesssteels, molybdenum, etc. The sheet of conductive material may be asubstantially continuous plane, or the sheet of conductive material maybe a mesh. The core layer 35 may be connected to the second terminals 14and carry a voltage such as power or ground to decouple noise fromsignal traces 43 on signal layers 34, 36, 37 (shown in FIG. 8).Furthermore, the core layer 35 gives the signal traces 43 above or belowa predictable impedance based on the dielectric constant of thedielectric, the geometry of the signal traces 43, and the height ofsignal traces 43 above or below the metal plane of the core layer 35.The core layer 35 may be pierced by vias 41 (shown in FIG. 7) allowingelectrical coupling of signal layers 34, 36, 37 on opposite sides of thecore layer 35. Furthermore, the core layer 35 may be coupled directly tothe first terminals 13 on the pad layer 33 through vias 41 to supplypower or ground to the wafer 1 under test.

In an alternate embodiment of the invention, the balancing layers 30 maybe electrically incorporated into the base unit 29 by routing activesignal traces on the balancing layers, and coupling the signal traces tothe first and second terminals 13 and 14 by vias 41 through the low CTEbase 31 or by a C-shaped flex circuit spanning the upper and lowersurfaces of the base unit 29. Furthermore, the balancing layers 30 couldsupport one or more active or passive circuits which facilitate theburn-in testing of wafers.

FIG. 7 depicts an inverted view of the pad layer 33. The pad layer 33has electrically conductive contact pads 38 disposed against adielectric layer 39. The contact pads 38 are dispersed across a surface40 of the dielectric layer 39 of the pad layer 33 and implement thefirst and second terminals 13 and 14 of the base unit 7 or 29. Pads 38may be raised above the surface of the dielectric, as shown, and mayhave any desired shape including circular, rectangular, conical, andtrapezoidal. In one embodiment of the invention, the contact pads 38 arecircular and made of a lower layer of copper with an outer coating ofnickel or gold to resist corrosion and reduce contact resistance.However, the outer material may be any noble metal, such as, but notlimited to, platinum or palladium. Similarly, the outer metal layer ofcontact pads 38 may also be any non-oxidative metal or metal alloy. Thecopper of the contact pads 38 is preferably formed from a base copperfoil by a subtractive etch process well known in the art. Subsequently,an outer coating may be formed onto the copper using any techniqueincluding plating by an electrolytic or electroless process. Vias 41 areshown formed in the dielectric layer 39 of the pad layer 33 beneath thecontact pads 38. Vias holes 41 may be formed in the dielectric layer 39by many known techniques including drilling and laser ablation.

Generally, various ePTFE-based dielectric materials can be laser drilledusing mode-locked solid states lasers operating in the UV range, and inparticular, those capable of producing energy densities in the range of0.5 to 20 J/cm² and those capable of making in-situ and virtuallyinstantaneous changes in the energy density by varying the pulserepetition rate from 1000 to 10000 Hz. These variations in pulserepetition rate result in variations in the pulse width for Nd:YAGlasers of between 40 and 100 ns. In general, when performing apost-pulse step to ablate dielectric residue after an initial ablationstep, the pulse density can be double for a brief time period, whereby1-10 pulses may typically

In one embodiment of the present invention, the blind vias are formedwith lasers that are solid state pulsed lasers such as the pulsed Nd:YAGlaser. The fundamental output from the Nd:YAG laser is at a wavelengthof 1064 nm. This wavelength is in the infrared portion of theelectromagnetic spectrum. By installing beta-Barium Borate (BBO)crystals in the optical path harmonic generation facilitates the outputof light at 355 nm (third harmonic) and 266 nm (fourth harmonic), whichfall in the ultraviolet range.

The 355 nm and 266 nm wavelengths are particularly well suited fordrilling vias in the laminated substrates of the present invention. Thepulse length, energy density and number of pulses can be varieddepending on the type of via being formed and the type of materials usedin the laminated substrate.

For example, for drilling blind vias in a laminated substrate made ofalternating layers of copper and an adhesive-filler-ePTFE dielectric,and using a 266 nm laser, the energy density is 1.5 J/cm², the energyper pulse is 10 μJ, and the power density is 20 megawatts per cm². Atthe 355 nm wavelength, blind vias are formed by setting the energydensity at 3.5 J/cm², the energy per pulse is 30 μJ, and the powerdensity is 35 megawatts per cm². The post-pulse step for the 355 nmblind via requires adjusting the conditions such that the energy densityis 11 J/cm², the energy per pulse is 100 μJ, and the power density is200 megawatts per cm².

When forming blind vias in the adhesive-filler-ePTFE dielectric, usingthe 355 nm laser, the energy density is 7 J/cm², the energy per pulse is65 μJ, and the power density is 100 megawatts per cm². A post-pulse stepwould require adjusting the parameters such that the energy density is11 J/cm², the energy per pulse is 100 μJ, and the power density is 200megawatts per cm² be used.

The via holes 41 may then be plated with a metal, for example copper, tocreate a conductive path from the contact pads 38 on the upper surface40 of the pad layer 33 to the lower surface 42 of the pad layer 33.

One or more signal layers, 34, 36, 37 is disposed above the pad layer33. However, the pad layer 33 is optional and the contact pads 38described as part of the pad layer 33 above may be implemented directlyon the signal layer 34. The signal layers 34, 36, 37 comprise aplurality of conductive segments or signal traces 93 distributed acrossa dielectric layer as shown in FIG. 8.

As seen in FIG. 8, the signal traces 43 create a conductive path 44between the first terminals 13 and the second terminals 14 of the baseunit 7 or 29. The signal traces 43 are typically and preferably copper,formed by a process of subtractive etching. A complete conductive pathfrom the first terminals 13 to the second terminals 14 may be formed bycreating a path from a first terminal 13, up through a via hole 91 (notshown) in the dielectric layer 39 of the pad layer 33 to a signal trace93 on a signal layer, across the signal trace 93 of the signal layer toanother via hole going down through the dielectric of the pad layer 33to a corresponding second terminal 14. Similarly, first and secondterminals 13 and 14 may be electrically connected by a more complex pathof signal traces 43 and vias 41 spanning multiple signal layers.

FIG. 9 depicts the low CTE base 31 according to one embodiment of theinvention. The base 31 is formed from a three ply stack of INVAR 36,copper and INVAR 36, respectively layers 45, 46 and 47. Instead of INVAR36, a nickel and iron alloy containing between 30 wt. % and 42 wt. %nickel may also be used. Additionally, in place of INVAR 36 and layers45 and 47, any low CTE material matched to the wafer unit test device,including but not limited to nickel alloys, may be used. The two nickelalloy sheets have a combined thickness t₁ and the copper sheet 46 has athickness t₂, wherein a ratio t₁ to t₂ is chosen to match thecoefficient of thermal expansion of a semiconductor wafer. The t₁ to t₂ratio can be between 4:1 and 14:1, including, but not limited to ratiosof 10:1, 11:1 and 12:1.

In one embodiment of the present invention, the nickel layers each havea thickness of approximately 115 mils, and the ratio of the nickellayers to the copper layer provides a coefficient of thermal expansionthat matches a silicon wafer. However, the ratio of the nickel layerthickness, or other material thickness, to the copper layer thicknessprovides a coefficient of thermal expansion for the base that matchesthe coefficient of thermal expansion for a wafer formed from germanium,silicon germanium, silicon carbide, gallium arsenide, selenium andtellurium.

Nickel alloys have a low coefficient of thermal expansion, and thereforeact to constrain the expansion of the base unit 31 relative to the wafer1 as temperature increases. Preferably a fourteen inch square sheet ofINVAR 36 and copper material are used. However, circular or rectangularsheets may be used. The sheets are between six and twenty inches indimension, i.e., diameter or side length, such as, eight, twelve,fourteen, sixteen and twenty inches.

The INVAR 36 and sheets 45 and 47 are each preferably machined toapproximately 115 mils thick with a degree of planarity between 0.020and 0.0001 inches per linear foot, preferably between 0.01 and 0.0001inches per linear foot. Most preferably, the degree of planarity is0.001 inches per linear foot.

The copper layer 46 is approximately 21 mils thick and has a planarityof 0.0005 inches per linear foot. The copper layer comprisesapproximately 8% to 10%, e.g., 9.1%, of the total thickness of saidmetal or metal alloy layers and said copper layer.

The stack of INVAR 36, copper, and INVAR 36 is formed by laminating eachpiece of INVAR 36 to a surface of the copper using a dielectric 48, suchas SPEEDBOARD® C., which is available from W. L. Gore and Associates,and which is described below. The dielectric layers of the low CTE baseare between 25 μm and 250 μm thick.

Sheet thicknesses of 115 mils and 21 mils of the nickel alloy and coppersheets respectively are used in one embodiment, but any dimensions maybe chosen, so long as the thickness of nickel alloy sheets is greaterthan the thickness of the copper.

DIELECTRIC:

The dielectric materials used for the base unit and wafer level contactsheet of the present invention can be any high temperature dielectricmaterial. For example, suitable dielectric materials include, but arenot limited to polyimides and polyimide laminates, epoxy resins, organicmaterials, or dielectric materials comprised at least in part ofpolytetrafluoroethylene, with or without a filler, where once theadhesive has been impregnated, it has been partially cured and forms aB-stage material. Suitable materials include SPEEDBOARD® bond pliesavailable from W. L. Gore and Associates, Inc. As should be understood,SPEEDBOARD® C does not contain a ceramic filler and is a prepreg ofnon-woven material containing a cyanate ester resin in apolytetrafluoroethylene matrix. SPEEDBOARD C® has a dielectric constant,(Dk) of about 2.6-2.7 at 1 MHz-10 GHz, a loss tangent of 0.004 at 1MHz-10 GHz, a dielectric strength greater than 1000 V/mil, a glasstransition and a T_(g) of 220° C., a resin content of 66-68 wt. % and isavailable in a variety of thicknesses.

Other classes of dielectric materials include those where a porousmatrix system contains an imbibed or impregnated adhesive-fillermixture. The porous matrix is a non-woven substrate that is imbibed withhigh quantities of filler and a thermoplastic or thermoset adhesive, asa result of the initial void volume of the substrate, heated topartially cure the adhesive and form a B-stage composite. Substratesinclude fluoropolymers, such as the porous expandedpolytetrafluoroethylene material of U.S. Pat. Nos. 3,953,566 to Gore and4,482,516 to Bowman, et al., each of which is incorporated herein byreference. Desirably, the mean flow pore size (MFPS) should be betweenabout 2 to 5 times or above that of the largest particulate, with a MFPSof greater than about 2.4 times that of the filler being particularlypreferred. However, it is also within the scope of the invention thatsuitable composites can be prepared by selecting the mean flow particlesize MFPS to average particle size ratio to be greater than 1.4.Acceptable composites can also be prepared when the minimum pore size toaverage particle size is at least above 0.8 or the minimum pore size tothe maximum particle size is at least above 0.4. The MFPS to particlesize ratio ratios being performed with a MICROTRAK FRA analyzer.

Alternatively, another mechanism for gauging relative pore and particlesizes may be calculated as the smallest pore size being not less thanabout 1.4 times the largest particle size.

In addition to expanded fluoropolymer substrates, porous expandedpolyolefins, such as ultra high molecular weight (UHMW) polyethylene,expanded polypropylene, polytetrafluoroethylene made prepared by pasteextrusion and incorporating sacrificial fillers, porous inorganic ororganic foams, microporous cellulose acetate, can also be used.

The porous substrate has an initial void volume of at least 30%,preferably at least 50%, and most preferably at least 70%, andfacilitates the impregnation of thermoset or thermoplastic adhesiveresin and particulate filler paste in the voids while providing aflexible reinforcement to prevent brittleness of the overall compositeand settling of the particles.

The filler comprises a collection of particles when analyzed by aMICROTRAK® Model FRA Partical Analyzer device, which displays a maximumparticle size, a minimum particle size and an average particle size byway of a histogram.

Suitable fillers to be incorporated into the adhesive include, but arenot limited to, BaTiO₃, SiO₂, Al₂ O₃, ZnO, ZrO₂, TiO₂, precipitated andsol-gel ceramics, such as silica, titania and alumina, non-conductivecarbon (carbon black) and mixtures thereof. Especially preferred fillersare SiO₂, ZrO₂, TiO₂ alone or incombination with non-conductive carbon.Most preferred fillers include filler made by the vapor metal combustionprocess taught in U.S. Pat. No. 4,705,762, such as, but not limited tosilicon, titanium and aluminum to produced silica, titania, and aluminaparticles that are solid in nature, i.e., not a hollow sphere, with auniform surface curvature and a high degree of sphericity.

The fillers may be treated by well-known techniques that render thefiller hydrophobic by silylating agents and/or agents reactive to theadhesive matrix, such as by using coupling agents. Suitable couplingagents include, silanes, titanates, zirconates, and aluminates. Suitablesilylating agents may include, but are not limited to, functionalsilyating agents, silazanes, silanols, siloxanes. Suitable silazanes,include, but are not limited to, hexamethyldisilazane (Huls H730) andhexamethylcyclotrisilazane, silylamides such as,bis(trimethylsilyl)acetamide (Huls B2500), silylureas such astrimethylsilylurea, and silylmidazoles such as trimethylsilylimidazole.

Titanate coupling agents are exemplified by the tetra alkyl type,monoalkoxy type, coordinate type, chelate type, quaternary salt type,neoalkoxy type, cycloheteroatom type. Preferred titanates include, tetraalkyl titanates, TYZOR® TOT {tetrakis(2-ethyl-hexyl) titanate, TYZOR®TPT {tetraisopropyl titanate}, chelated titanates, TYZOR® GBA {titaniumacetylacetylacetonate}, TYZOR® DC {titanium ethylacetacetonate}, TYZOR®CLA {proprietary to DuPont}, Monoalkoxy (KEN-REACT® KR TTS), KEN-REACT®,KR-55 tetra (2,2 diallyloxymethyl)butyl, di(ditridecyl)phosphitotitanate, LICA® 38 neopentyl(diallyl)oxy, tri(dioctyl)pyro-phosphatotitanate.

Suitable zirconates include, any of the zirconates detailed at page 22in the Kenrich catalog, in particular KZ 55-tetra (2,2diallyloxymethyl)butyl, di(ditridecyl)phosphito zirconate,NZ-01-neopentyl(diallyl)oxy, trineodecanoyl zirconate,NZ-09-neopentyl(diallyl)oxy, tri(dodecyl)benzene-sulfonyl zirconate.

The aluminates that can be used in the present invention include, butare not limited to KENRICH®, diisobutyl(oleyl)acetoacetylaluminate (KA301), diisopropyl(oleyl)acetoacetyl aluminate (KA 322) and KA 489.

In addition to the above, certain polymers, such as, cross-linkedvinylic polymers, e.g., divinylbenzene, divinyl pyridine or a sizing ofany of the disclosed thermosetting matrix adhesives that are firstapplied at very high dilution (0.1 up to 1.0% solution in MEK) can beused. Also, certain organic peroxides, such as, dicumylperoxide can bereacted with the fillers.

The adhesive itself may be a thermoset or thermoplastic and can includepolyglycidyl ether, polycyanurate, polyisocyanate, bis-triazine resins,poly (bis-maleimide), norbornene-terminated polyimide, polynorbornene,acetylene-terminated polyimide, polybutadiene and functionalizedcopolymers thereof, cyclic olefinic polycyclobutene, polysiloxanes, polysisqualoxane, functionalized polyphenylene ether, polyacrylate, novolakpolymers and copolymers, fluoropolymers and copolymers, melaminepolymers and copolymers, poly(bis phenycyclobutane), and blends orprepolymers thereof. It should be understood that the aforementionedadhesives may themselves be blended together or blended with otherpolymers or additives, so as to impact flame retardancy or enhancedtoughness.

As used herein, Mean Flow Pore Size and minimum pore size weredetermined using the COULTER® Porometer II (Coulter Electronics Ltd.,Luton UK) which reports the value directly. Average particle size andlargest particle size were determined using a Microtrac light scatteringparticle size analyzer Model No. FRA (Microtrac Division of Leeds &Northup, North Wales, Pa., USA). The average particle size (APS) isdefined as the value at which 50% of the particles are larger. Thelargest particle size (LPS) is defined as the largest detectableparticle on a Microtrac histogram. Alternatively, the largest particlesize is defined at the minimum point when the MICROTRAK FRA determinesthat 100% of the particulate have passed.

In general, the method for preparing the adhesive-filler delectircinvolves:(a) expanding a polytetrafluoroethylene sheet by stretching alubricated extruded perform to a microstructure sufficient to allowsmall particles and adhesives to free flow into the void or pore volume;(b) forming a paste from polymeric, e.g., thermoset or thermoplasticmaterial and a filler; and (c) imbibing by dipping, coating, pressurefeeding, the adhesive-filler paste into the highly porous scaffold, suchas expanded polytetrafluoroethylene.

To prepare the filled adhesive film of this invention, particulatefiller is mixed into a solvent or aqueous solution or molten adhesive toafford a finely dispersed mixture. The filler in small particle form isordinarily less than 40 microns in size, and preferably has an averageparticulate size between 1 and 10 microns. The mean pore size of thenode-and-fibril structure of the polytetrafluoroethylene should be largeenough to allow for adequate penetration of the particulate. If thesubstrate is to be expanded polytetrafluoroethylene, then structuressimilar to those taught in U.S. Pat. No. 4,482,516 to Bowman, et al. aredesirable. Desirably, the mean flow pore size (MFPS) should be betweenabout 2 to 5 times or above that of the largest particulate, with a MFPSof greater than about 2.4 times that of the filler being particularlypreferred. However, it is also within the scope of the invention thatsuitable composites can be prepared by selecting the mean flow particlesize MFPS to average particle size ratio to be greater than 1.4.Acceptable composites can also be prepared when the minimum pore size toaverage particle size is at least above 0.8 or the minimum pore size tothe maximum particle size is at least above 0.4. The MFPS to particlesize ratio ratios being performed with a MICROTRAK FRA analyzer.

Alternatively, another mechanism for gauging relative pore and particlesizes may be calculated as the smallest pore size being not less thanabout 1.4 times the largest particle size.

Table 1 shows the effect of the relationship of the substrate mean flowpore size (MFPS) and particulate size. When the ratio of the mean flowpore size (MFPS) to largest particulate is 1.4 or less, poor results areobserved. In this case, a homogeneous composite is not observed, andmost of the particulate filler does not uniformly penetrate themicroporous substrate. When the ratio of the MFPS to largest particulateis greater than about 2.0, then a uniform composite is obtained. It isalso observed that the larger the ratio of MFPS to largest particulate,the greater the relative case it is to imbibe a homogeneous dispersioninto the microporous substrate.

                  TABLE 1                                                         ______________________________________                                        Substrate   Particle                                                          Pore Size   Size      MFPS    Pore.sub.Min                                                                        Pore.sub.Min                              Sam- Min    MFPS    Avg  Max  ÷ ÷ ÷ Re-                             ple (μm) (μm) (μm) (μm) Part.sub.Avg Part.sub.Max Part.sub.A                                                    vg sult                       ______________________________________                                        A    4      7       5    10   1.4   0.4   0.8   Poor                            B 4 5 5 10 1.0 0.4 0.8 Poor                                                   C --  58 5 10 12.4 N/A --  Good                                               D 18 32 6 10 5.3 1.8 3.0 Good                                                 E 18 32 1 1 32.0 18.0 18 Good                                                 F 17 24 6 10 4.0 1.7 2.8 Good                                                 G 0.2 0.4 0.5 1.6 0.8 0.125 0.4 Poor                                          H --  60 18 30 3.3 --  --  Good                                               I 14 11 0.5 1.6 22.0 8.8 28 Good                                              J 14 29 4 8 7.3 1.8 3.5 Good                                                  K 14 29 5 10 5.8 1.4 2.8 Good                                               ______________________________________                                    

EXAMPLE 1

A fine dispersion was prepared by mixing 281.6 g TiO₂ (TI Pure R-900, DuPont Company) into a 20% (w/w) solution of a flame retardeddicyanamide/2-methylimidazole catalyzed bisphenol-A based polyglycidylether (Nelco N-4002-5, Nelco Corp.) in MEK. The dispersion wasconstantly agitated so as to insure uniformity. A swatch of expandedPTFE was then dipped into the resin mixture. The web was dried at 165°C. for 1 min. under tension to afford a flexible composite. Thepartially-cured adhesive composite thus produced comprised of 57 weightpercent TiO₂, 13 weight percent PTFE and 30 weight percent epoxyadhesive. Several plies of the adhesive sheet were laid up betweencopper foil and pressed at 600 psi in a vacuum-assisted hydraulic pressat temperature of 225° C. for 90 min. then cooled under pressure. Thisresulted in a copper laminate having dielectric constant of 19.0, andwithstood a 30 sec. solder shock at 280° C. at an average ply thicknessof 100 mm (0.0039"(3.9 mil)) dielectric laminate thickness.

EXAMPLE 2

A fine dispersion was prepared by mixing 386 g SiO₂ (HW-11-89, HarbisonWalker Corp.) which was pretreated with phenyltrimethoxysilane (04330,Huls/Petrarch) into a manganese catalyzed solution of 200 g bismaleimidetriazine resin (BT206OBJ, Mitsubishi Gas Chemical) and 388 g MEK. Thedispersion was constantly agitated so as to insure uniformity. A swatchof 0.0002" thick expanded PTFE was then dipped into the resin mixture,removed, and then dried at 165° C. for 1 min. under tension to afford aflexible composite. Several plies of this prepreg were laid up betweencopper foil and pressed at 250 psi in a vacuum-assisted hydraulic pressat temperature of 225° C. for 90 min. then cooled under pressure. Thisresulting dielectric thus produced comprised of 53 weight percent SiO₂,5 weight percent PTFE and 42 weight percent adhesive, displayed goodadhesion to copper, dielectric constant (at 10 GHz) of 3.3 anddissipation factor (at 10 GHz) of 0.005.

EXAMPLE 3

A fine dispersion was prepared by mixing 483 g SiO₂ (HW-11-89) into amanganese-catalyzed solution of 274.7 g bismaleimide triazine resin(BT206OBJ, Mitsubishi Gas Chemical) and 485 g MEK. The dispersion wasconstantly agitated so as to insure uniformity. A swatch of 0.0002"thick expanded PTFE was then dipped into the resin mixture, removed, andthen dried at 165° C. for 1 min. under tension to afford a flexiblecomposite. Several plies of this prepreg were laid up between copperfoil and pressed at 250 psi in a vacuum-assisted hydraulic press attemperature of 225° C. for 90 minutes then cooled under pressure. Theresulting dielectric thus produced comprised of 57 weight percent SiO₂,4 weight percent PTFE and 39 weight percent adhesive, displayed goodadhesion to copper, dielectric constant (at 10 GHz) of 3.2 anddissipation factor (at 10 GHz) of 0.005.

EXAMPLE 4

A fine dispersion was prepared by mixing 15.44 kg TiO₂ powder (TI PureR-900, DuPont Company) into a manganese-catalyzed solution of 3.30 kgbismaleimide triazine resin (BT206OBH, Mitsubishi Gas Chemical) and15.38 kg MEK. The dispersion was constantly agitated so as to insureuniformity. A swatch of 0.0004" TiO₂ -filled expanded PTFE (filledaccording to the teachings of Mortimer U.S. Pat. No. 4,985,296, exceptto 40% loading of TiO₂ and the membrane was not compressed at the end)was then dipped into the resin mixture, removed, and then dried at 165°C. for 1 min. under tension to afford a flexible composite. Thepartially cured adhesive composite thus produced comprised of 70 weightpercent TiO₂, 9 weight percent PTFE and 21 weight percent adhesive.Several plies of this prepreg were laid up between copper foil andpressed at 500 psi in a vacuum-assisted hydraulic press at temperatureof 220° C. for 90 minutes then cooled under pressure. This resultingdielectric displayed good adhesion to copper, dielectric constant of10.0 and dissipation factor of 0.008.

EXAMPLE 5

A fine dispersion was prepared by mixing 7.35 kg SiO₂ (ADMATECHS SO-E2,Tatsumori LTD) with 7.35 kg MEK and 73.5 g of coupling agent, i.e.,3-glycidyloxypropyltri-methoxysilane (Dynasylan GLYMO (Petrach Systems).SO-E2 is described by the manufacture as having highly spherical silicahaving a particle diameter of 0.4 to 0.6 mm, a specific surface area of4-8 m² /g, a bulk density of 0.2-0.4 g/cc (loose).

To this dispersion was added 932 g of a 50% (w/w) solution of a cyanatedphenolic resin, Primaset PT-30 (Lonza Corp.). In (MEK)methylethylketone, 896 g of a 50% (w/w) solution of RSL 1462 (ShellResins, Inc.(CAS #25068-38-6)) in MEK, 380 g of a 50% (w/w) solution ofBC-58 (Great Lakes, Inc.) in MEK, 54 g of 50% solution of bisphenol A(Aldrich Company) in MEK, 12.6 g Irganox 1010 (Ciba Geigy), 3.1 g of a0.6% solution of Manganese 2-ethylhexanoate (Mn HEX-CEM (OMG Ltd.), and2.40 kg MEK. This dispersion was subjected to ultrasonic agitationthrough a Misonics continuous flow cell for about 20 minutes at a rateof about 1-3 gal./minute. The fine dispersion thus obtained was furtherdiluted to an overall bath concentration of 11.9% solids (w/w).

The fine dispersion was poured into an impregnation bath. A expandedpolytetrafluoroethylene web having the node fibril structure of FIG. 5,and the following properties:

    ______________________________________                                        Frazier          20.55                                                          Coverage 9 g/m.sup.2                                                          Ball Burst 3.2 lbs.                                                           Thickness 6.5 mil.                                                            Mean Flow Pore Size 9.0 microns                                             ______________________________________                                    

The Frazier number relates to the air permeability of the material beingassayed. Air permeability is measured by clamping the web in a gasketedfixture which is provided in circular area of approximately 6 squareinches for air flow measurement. The upstream side was connected to aflow meter in line with a source of dry compressed air. The downstreamside of the sample fixture was open to the atmosphere. Testing isaccomplished by applying a pressure of 0.5 inches of water to theupstream side of the sample and recording the flow rate of the airpassing through the in-line flowmeter (a ball-float rotameter that wasconnected to a flow meter.

The Ball Burst Strength is a test that measures the relative strength ofsamples by determining the maximum at break. The web is challenged witha 1 inch diameter ball while being clamped between two plates. TheChatillon, Force Gauge Ball/Burst Test was used. The media is plaacedtaut in the measuring device and pressure afixed by raising the web intocontact with the ball of the burst probe. Pressure at break is recorded.

The web described above was passed through a constantly agitatedimpregnation bath at a speed at or about 3 ft./min, so as to insureuniformity. The impregnated web is immediately passed through a heatedoven to remove all or nearly all the solvent, and is collected on aroll.

Several plies of this prepeg were laid up between copper foil andpressed at 200 psi in a vacuum-assisted hydraulic press at temperatureof 220° C. for 90 minutes and then cooled under pressure. This resultingdielectric displayed good adhesion to copper, dielectric constant (10GHz) of 3.0 and dissipation factor of 0.0085 (10 GHz).

The physical properties of the particulate filler used in Example 4 andExample 7 are compared below.

    ______________________________________                                        Property      Tatsumori   Harbison Walker                                        (ADMATECHS)                                                                  Manufacture Technique Vapor Metal Amorphous Fused Silica                       Combustion                                                                   Designation Silica SO-E2 HW-11-89                                             Median Particle Size 0.5 micron 5 micron                                      Shape Spherical Irregular, jagged                                             Surface Area 6-10 m.sup.2 /g 10m.sup.2 /g                                     Bulk Density 0.47 g/cc 1.12 g/cc                                              Specific Density 2.26 g/cc 2.16 g/cc                                        ______________________________________                                    

EXAMPLE 6

An ePTFE matrix containing an impregnated adhesive filler mixture, basedon SiO₂ prepared from the vapor combustion of molten silicon is preparedas follows. Two precursor mixtures were initially prepared. One being inthe form of a slurry containing a silane treated silica similar to thatof Example 5 and the other an uncatalyzed blend of the resin and othercomponents.

Mixture I

The silica slurry is a 50/50 blend of the SO-E2 silica of Example 5 inMEK, where the silica contains a coated of silane which is equal to 1%of the silica weight. To a five gallon container, 17.5 pounds of MEK and79 grams of silane were added and the two components mixed to ensureuniform dispersion of the silane in the MEK. Then, 17.5 pounds of thesilica of Example 5 were added. Two five gallon containers of theMEK-silica-silane mixture were added to a reaction vessel, and thecontents, i.e., the slurry, was recirculated through an ultrasonicdisperser for approximately one hour to break up any silica agglomeratesthat may be present. The sonication was completed and the contents ofthe reaction vessel were heated to approximately 80° C. forapproximately one hour, while the contents were continuously mixed. Thereacted mixture was then transferred into a ten gallon container.

Mixture II

The desired resin blend product is an MEK based mixture containing anuncatalyzed resin blend (the adhesive) contains approximately 60%solids, where the solid portion is an exact mixture of 41.2% PT-30cyanated phenolic resin, 39.5% RSL 1462 epoxy resin, 16.7% BC58 flameretardant, 1.5% Irganox 1010 stabilizer, and 1% bisphenol A co-catalyst,all percentages by weight.

Into a ten gallon container, 14.8 pounds of PT-30 and 15-20 pounds ofMEK were added and stirred vigorously to completely solvate the PT-30.Then 6 pounds of BC58 were measured and added to the MEK/PT-30 solutionand vigorously agitated to solvate the BC58. The stabilizer, 244.5 gramsof Irganox 1010 and bisphenol A, 163 grams were added. The ten galloncontainer was reweighed and 14.22 pounds of RSL 1462 were added.Additional MEK was added to bring the mixture weight to 60 pounds. Thecontents were then vigorously agitated for approximately 1 to 2 hours,or as long is necessary to completely dissolve the solid components.

The desired product is a mixture of the silica treated with a silane,the uncatalyzed resin blend, and MEK in which 68% by weight of thesolids are silica, and the total solids are between 5% and 50% by weightof the mixture. The exact solids concentration varies from run to run,and depends in part on the membrane to be impregnated. The catalystlevel is 10 ppm relative to the sum of the PT-30 and RSL 1462.

The solid contents of mixtures I and II were determined to verify theaccuracy of the precursors and compensate for any solvent flash that hadoccurred. Then mixture I was added to a ten gallon container to provide12 pounds of solids, e.g., 515 solids content, 23.48 pounds of mixtureI. Then mixture II was added to the container to provide 5.64 pounds ofsolids, e.g., 59.6% solids, 9.46 pounds of mixture II. the manganesecatalyst solution (0.6% in mineral spirits), 3.45 grams, was added tothe mixture of mixture I and mixture II and blended thoroughly to form ahigh solids content mixture.

The bath mixture for impregnating an ePTFE matrix, 28% solids mixture,was prepared by adding sufficient MEK to the high solids content mixtureto a total weight of 63 pounds.

Thereafter, an ePTFE matrix weas impregnated with this bath mixture toform a dielectric material.

EXAMPLE 7

A fine dispersion was prepared by mixing 26.8 grams Furnace Black(Special Schwarz 100, Degussa Corp., Ridgefield Park, New Jersey) and 79grams of coupling agent (Dynaslan GLYMO CAS #2530-83-8;3-glycidyloxypropyl-trimethoxysilane (Petrach Systems). The dispersionwas subjected to ultrasonic agitation for 1 minute, then added to astirring dispersion of 17.5 pounds SiO₂ (SO-E2) in 17.5 pounds MEK whichhad previously been ultrasonically agitated. The final dispersion washeated with constant overhead mixing for 1 hour at reflux, then allowedto cool to room temperature.

Separately, an adhesive varnish was prepared by adding the following:3413 grams of a 57.5% (w/w) mixture of Primaset PT-30 in MEK, 2456 gramsof a 76.8% (w/w/) mixture of RSL 1462 in MEK, 1495 grams of a 53.2%(w/w) solution of BC58 (Great Lakes, Inc.) in MEK, 200 grams of 23.9%(w/w) solution of bisphenol A (Aldrich Company) in MEK, 71.5 gramsIrganox 1010, 3.21 grams of a 0.6% (w/w) solution of Mu HEX-CEM (OMGLtd.) in mineral spirits, and 2.40 kg MEK.

In a separate container, 3739 grams of the dispersion described abovewas added, along with 0.0233 grams of Furnace Black (Special Schwarz100, Degussa Corp., Ridgefield Park, New Jersey), 1328 of the adhesivevarnish described above and 38.3 pounds MEK. This mixture was pouredinto an impregnation bath, and an ePTFE web was passed through theimpregnation bath at a speed at or about 3 ft/min. This dispersion wasconstantly agitated so as to insure uniformity. The impregnated web isimmediately passed through a heated oven to remove all or nearly all thesolvent, and is collected on a roll.

Several piles of this prepeg were laid up between copper foil andpressed at 200 psi in a vacuum-assisted hydraulic press at temperaturesof 200° C. for 90 minutes then cooled under pressure. This resultingdielectric displayed good adhesion to copper.

EXAMPLE 8

An adhesive varnish was prepared by adding the following: 3413 grams ofa 57.5% (w/w) solution of Primaset PT-30 (PMN P-88-1591)) in MEK, 2456grams of a 76.8% (w/w) solution of RSL 1462 in MEK, 1495 grams of a53.2% (w/w) solution of BC58 (Great Lakes, Inc.) in MEK, 200 grams of23.9% (w/w) solution of bisphenol A (Aldrich Company) in MEK, 71.5 gramsIrganox 1010, 3.21 grams of a 0.6% (w/w) solution of Mn HEX-CEM inmineral spirits, and 2.40 kg MEK.

In a separate container, 1328 grams of the adhesive varnish describedabove, 42.3 pounds MEK, 6.40 grams of Furnace Black (Special Schwarz100, Degussa Corp., Ridgefield, New Jersey) and 1860.9 grams SiO₂(SO-E2). This mixture was poured into an impregnation bath, and an ePTFEweb was passed through the impregnation bath at a speed at or about 3ft/min. The dispersion was constantly agitated so as to insureuniformity. The impregnated web is immediately passed through a heatedoven to remove all or nearly all the solvent, and is collected on aroll.

Several piles of this prepeg were laid up between copper foil andpressed at 200 psi in a vacuum-assisted hydraulic press at temperatureof 220° C. for 90 minutes then cooled under pressure. This resultingdielectric displayed good adhesion to copper.

The low CTE base of FIG. 9 was prepared using the dielectric material ofExample 6. A copper core was laminated on each side thereof with a layerof the filled ePTFE of FIG. 9. Thereafter, INVAR 36 is placed on eachexposed side of the dielectric material. The composite is heated underpressure to form the base unit 31.

As discussed above with reference to FIGS. 1 and 2, a Z-axis material isused for components 2 and 9. The selectively conductive Z-axis substratemember is reusable and compliant. As taught in U.S. Pat. No. 5,498,467to Meola, the basic substrate is a planar, open cell, porous materiallying in a plane defined by an x and a y-axis, and having Z-axispathways extending from one side of the material to the other side. Whenthe Z-axis material includes an optional elastomer, it is positionedbetween the lower surface 12 of the base unit 7 and the upper surface ofthe laminated wafer level contact sheet 9. The selectively conductivemember 8, having the optional elastomer, has a series of electricallyisolated, irregularly shaped electrically conductive pathways extendingfrom a lower surface of the selectively conductive member to an uppersurface generally in the direction of the Z-axis. When in place betweenthe base unit 7 and the laminated wafer level contact sheet 9, theelectrically conductive pathways electrically couple the first terminals13 of the base unit 7 to the contact pads 20 on the upper surface of thelaminated wafer level contact sheet 9.

When the Z-axis material is used to form the laminated wafer levelcontact sheet 9, to be described hereinafter, it contains an bondingadhesive which is in the partially cured, B-stage. However, because itis in contact with the Z-axis material 8, is may be readily detachedtherefrom and be reused to attach another wafer level contact sheet 9.

Suitable materials for the Z-axis member, which can be used for both thematerial 8 and laminated wafer level contact sheet 9, have a thicknesson the order of 5×10⁻⁶ m and 5×10⁻⁴ m (5 μm and 500 μm), e.g, 50 μm, 75μ, 100 μm, 150 μm etc., and include woven or non-woven fabric, such as anylon, glass fiber or polyester fabric or cotton, or the like. Themember can also be a porous polymeric material or membrane, that isflexible, such as porous polyolefins, e.g., porous polyethylene, porouspolypropylene, porous fluoropolymers, or open cell, porouspolyurethanes. Additionally, open cell, porous inorganic materials, suchas thin porous ceramic plates that have continuous pores from one sideto the other can be used.

Porous fluoropolymers include, but are not limited to, porouspolytetrafluoroethylene (PTFE), porous expanded polytetrafluoroethylene(ePTFE), porous copolymers of polytetrafluoroethylene and polyesters orpolystyrenes, copolymers of tetrafluoroethylene and fluorinated ethylenepropylene (FEP) or perfluoroalkoxy -tetrafluoroethylene (PFA) with a C₁-C₄ alkoxy group. Porous materials include expanded polypropylene,porous polyethylene and porous polytetrafluoroethylene.

The material used as the substrate for the Z-axis material is expandedpolytetrafluoroethylene having a microstructure of nodes interconnectedwith fibrils, a void volume of about 20% to 90%, such as the materialprepared in accordance with the teachings of U.S. Pat. No. 3,953,566,incorporated herein by reference, exemplified by the ePTFE of FIG. 11.

A planar porous material that is used as the Z-axis substrate has athickness of between about 5 and 125 μm, but thickness is not a criticalfactor so long as the ultra-violet strength used to form the conductivepathways will penetrate the sample.

With reference to FIGS. 10-13, when the material for forming the Z-axismember is microporous PTFE (expanded polytetrafluoroethylene), the pores49 are defined as the space between nodes 50 interconnected with fibrils51, as shown in FIG. 10. In this case, the internal structure of nodes50 interconnected with fibrils 51 is of a material density that resultsin an irregular continuous path 52 through the Z axis within avertically defined cross section of the Z axis from one side of theplanar member to the other (see FIG. 13).

The selectively conductive member 53 (FIG. 13) is prepared by makingareas 32 (FIG. 12) through the Z-axis direction receptive to depositionof a metal salt, which metal salt on exposure to radiant energy isconverted to nonconductive metal nuclei which then act to catalyzedeposition of a conductive metal from an electroless metal depositionsolution. The pores 49 of a porous member, defined above, are firstwetted with a wetting agent, such as an alcohol, or organic aqueoussurfactant. Methanol, propanol, tetrafluoroethylene/vinyl alcoholcopolymers or the like may be used. The wetting agent acts to make thematerial of the member receptive to conductive metals such as nickel orcopper.

A radiation sensitive metal salt composition is a liquid radiationsensitive composition comprising a solution of a light sensitivereducing agent, a metal salt, a source of halide ions, and a secondreducing agent. Preferably, the radiation sensitive solution containswater, the metal salt, a light sensitive reducing agent, a secondreducing agent, and optionally (for hard to wet surfaces) a surfactant.The metal salt includes but is not limited to, copper acetate, copperformate, copper bromide, copper sulfate, copper chloride, nickelchloride, nickel sulfate, nickel bromide, ferrous bearing compounds,such as, ferrous sulfate, ferrous chloride, and noble metals such aspalladium, platinum, silver, gold and rhodium.

Suitable light-sensitive reducing agents are aromatic diazo compounds,iron salts, e.g., ferrous or ferric oxalate, ferric ammonium sulfate,dichromates e.g., ammonium dichromate, anthraquinone disulfonic acids orsalts thereof, glycine (especially active under humid surfaceconditions), L-ascorbic acid, azide compounds, and the like, as well asmetal accelerators, e.g., tin compounds, e.g., stannous chloride orcompounds of silver, palladium, gold, mercury, cobalt, nickel, zinc,iron, etc., the latter group optionally being added in amounts of 1 mgto 2 grams per liter.

The second reducing agents, include, but are not limited to, polyhydroxyalcohols, such as glycerol, ethylene glycol, pentaerythritol,mesoerythritol, 1,3-propanediol, sorbitol, mannitol, propylene glycol,1,2-butanediol, pinacol, sucrose, dextrin, and compounds such astriethanolamine, propylene oxide, polyethylene glycols, lactose, starch,ethylene oxide and gelatin. Compounds which are also useful as secondaryreducing agents are aldehydes, such as formaldehyde, benzaldehyde,acetaldehyde, n-butyraldehyde, polyamides, such as nylon, albumin andgelatin; leuco b ases of triphenyl methane dyes, such as4-dimethylaminotriphenylmethane,4',4',4"-tri-di-methylamino-triphenylmethane; leuco bases of xanthenedyes, such as 3,6-bis dimethylamino xanthene and 3,6-bisdimethylamino-9-(2-carboxyethyl) xanthene; polyethers, such as ethyleneglycol diethyl ether, diethylene glycol, diethyl ether tetraethyleneglycol dimethyl ether, and the like.

A second reducing agent that is also a humectant, exemplified bysorbitol, as a constituent of the treating solution, for the humectant,apparently by reason of a moisture conditioning effect on the "dry"coating prior to developing. It provides substantial aid in maintainingdensity of the metal coating on the internal material of the memberduring a developing step in which any unconverted radiation-sensitivecomposition in the coating is washed off of the base.

Among the suitable surfactants are polyethenoxy nonionic ethers, such asTriton X-100, manufactured by Rohm & Haas Co., and nonionic surfactantsbased on the reaction between nonyl phenol and glycidol, such asSurfactants 6 G and 10 G manufactured by Olin Mathieson Company.

This treating solution, i.e., the radiation sensitive composition,contains an acidifying agent in the form of an acid salt for adjustingthe pH of the aqueous solution to usually between about 2.0 and 4.0(preferably 2.5 to 3.8) and a small quantity of halide ions (iodide,bromide or chloride ions), so that a combination of additives provides asurprising effect in substantially intensifying the density of thecoating that is formed subsequently by exposure of the treated planarmaterial to radiant energy. Adjusting the acidity does not alwaysrequire introducing an agent for that purpose alone, because theadjustment may be accomplished wholly or partially by means of an acidicsubstance that has other functions also, as exemplified by alight-sensitive reducing agent of an acidic nature (e.g., ascorbic acid,glycerin, etc.) or by some additives for introducing halide ions (e.g.,hydrochloric acid). Similarly, some or all of the halide ions may beintroduced as components of the reducible metal salt (e.g., cupricchloride).

Among the many suitable acidic substances which may be employed incontrolling or adjusting the pH of the sensitizing solution arefluoroboric acid, citric acid, lactic acid, phosphoric acid, sulfuricacid, acetic acid, formic acid, boric acid, hydrochloric acid, nitricacid and the like. A wide variety of bromide, chloride and iodide saltand other halide-generating water soluble compounds may be utilized toprovide part or all of the desired halide ion content of the treatingsolution. These may include, inter alia, salts of metals in general andthese halogens as exemplified by cupric bromide, nickel chloride, cobaltchloride, cupric chloride, sodium iodide, potassium iodide, lithiumchloride, magnesium iodide, magnesium bromide, sodium bromide, potassiumbromide, and the like. Bromide salts are suitable, as they produce ahigher degree of sensitivity (i.e., darker and denser deposits) on thesubstrate than the corresponding chloride in at least certain instances.

The halide ions constitute only a minor proportion of the solute and maytypically range from about 0.045 to 1.6%, preferably about 0.13 to0.45%, based on the total weight of dissolved solids. The amount ofhalogen may be stated otherwise as between about 0.9 and 25milli-equivalents of halogen per liter of the sensitizing solution,preferably about 2.5 to 9 milliequivalents, e.g., 0.3-1.0 gm/l forcupric bromide. Increasing the proportions of the halide ions is usuallyundesirable as such increases appear to gradually diminish thesensitizing effect of the treatment below what is obtainable with theoptimum amount. Also, the proportion of these halide ions expressed asequivalents is less than that of the cupric or other reducible non-noblemetal cations in the treating solution. For instance, the ratio ofequivalents of such metal ions to halide ions is usually in the range ofat least 2:1 and preferably about 4:1 to 100:1.

The radiation sensitive composition is applied to the material tothoroughly wet the material defining the pores whereby the porous memberis subjected to the radiation sensitive composition for a timesufficient for the composition to permeate or penetrate through thepores of the material and form a coating on the pore interior along thematerial defining the pores from one side of the porous planar materialto the other. Thereafter the coating porous member is dried by airdrying or oven baking at below 50° C. At this stage, to preserve thelight-sensitive nature of the treating compositions, the material shouldbe processed under yellow light conditions. The member should also bekept at a temperature less than 70° F. and at no greater than 60%relative humidity because of possible absorption of water by thematerial of the member which can adversely affect the process.

The surface of one side of the coated porous member is masked with anopaque cover 55 (FIG. 11) in selected areas so that subsequent radiationwill not strike the covered area. The masking can result in dot shapedconductive areas of any desired, shape, size, array or alternating bandsor strips of conductive areas through the Z axis direction, separated byalternating bands of nonconductive areas (electrically isolating), foruse as an electrical connector. The dots are conventionally circulator,but could have other geometrical configurations, as squares, rectangles,etc. The size of the dot can be as small as a 0.0001 inches and as largeas 0.025 inches, preferably 0.001 inches, 0.002 inches, 0.003 inches,0.004 inches, 0.005 inches, 0.008 inches, 0.009 inches or fractionthereof where the pitch, defined as the distance between the centers ofadjacent dots is preferably at least twice the dimension of the dots,e.g., 1 mil dot, 2 mil pitch.

The masked member of FIG. 11 is exposed to radiation, such as light,electron beams, x-ray, and the like, preferably ultraviolet radiation,for a time and at a power sufficient to reduce the metallic cations inthe metal salt to metal nuclei throughout the thickness of the member.The member is then unmasked and washed with an acidic or alkalinewashing solution to wash off the radiation sensitive composition thathad been protected by the opaque cover. The acidic or alkaline washing(or fixing) solution does not affect the areas where the radiation hadreduced the metal cations to metal nuclei, if the solution is not leftin contact with the areas for more than a few minutes, e.g., 5 minutesor less.

Specifically, the treated member is selectively masked with a metallicmask, diazo or silver halide film, as shown in FIG. 11. The maskedmember is then photo imaged with either a non-collimated or collimatedultra-violet light source of less than 500 manometers wavelength. Thecatalyst, the nonconductive metal nuclei, itself requires a minimum of200 millijoules radiant energy to establish a stable photo image.

The UV light energy is strong enough to penetrate through the thicknessof the porous member. Thus, in subsequent plating operations, theconductive metal plates continuously through the Z-axis and provideselectrical continuity in the Z-axis. If desired, the UV light energy canbe applied to both sides of the planar member.

After a 5 minute normalization period, the catalyzed material is thenwashed for a short period of 30-90 seconds in a sulfuric acid solution,e.g. a solution consisting of 8% sulfuric acid by weight and 92%deionized water by weight or an alkaline solution consisting of 40 g/Iof ethylene diamine tetraacetic acid, 100 ml/I of formaldehyde, adjustedat a pH of greater than 10 with sodium hydroxide. The purpose of thiswashing step is to eliminate the unexposed catalyst from the materialwhile retaining the photo-reduced image.

The washed material containing the selective image is next stabilizedwith a reactive metal cation replacement solution. A convenient solutionis:

    ______________________________________                                        REACTIVE METAL CATION SOLUTION                                                ______________________________________                                        0.25 gram/liter of palladium chloride                                           8% sulfuric acid by weight                                                    92% D.I. water by weight                                                    ______________________________________                                    

The image undergoes a replacement reaction of the copper with morestable cation, e.g., palladium. A more stable system is desired becauseof the tendency of the copper to oxidize at such thin layer amounts andbecause of the ability of the palladium to more rapidly initiate thereduction reaction in the electroless bath. The member is kept in thissolution at least 30 seconds, and is subsequently washed in D.I. waterfor about 1 minute.

The catalyzed member is selectively electrolessly plated with one ormore conductive metals to a deposition thickness of about 50-60 microinches. Such metals include copper, nickel, gold, silver, platinum,cobalt, palladium, rhodium, aluminum and chromium. During the time inthe electroless baths, the member is agitated with a rocking motion topromote diffusion of the metal to the innermost region of the substrate.Plating is carried out by first rinsing in deionized water, then dippingin an agitated electroless copper bath for a time sufficient to depositcopper in the material over the palladium and through the substratethickness. Thus, within selected areas through the material in the Zaxis direction, the material nodes 50 and fibrils 51 are at leastpartially covered with a conductive metal layer 56, having a Z-axisportion 57 and upper and lower contact pads 58 and 59. See FIG. 13. Thisthe conductive metal 56 forms a continuous path of conductivity 24through the selected areas between upper and lower pads 58 and 59.

If the Z-axis material is to be used as member 8, then it may be imbibedwith an elastomer 60 which fills the previous designated pores 49. Theelastomer can include any material that has elastomeric properties, suchas, but not limited to siloxanes (silicon) based elastomers, acrylics,butyl rubbers, chlorosulfonated polyethylene, ethylene-propylene rubber,fluorinated elastomers, and thermoplastic rubbers includingpolystyrenes, polyethylenes, neoprenes, and polybutadiane. Preferablythe elastomer is DOW CORNING® 3-1753 which is, as supplied, atranslucent liquid having a use range of -55° C. to 200° C., and at 25°C. has a specific gravity of 0.98 and a viscosity of 385 cps at 25° C.The conformal coating of DOW CORNING® 3-1753 cures to a siliconeelastomer that will not melt or appreciably soften. Other elastomers areDOW CORNING® 3-1765, which as supplied, is translucent and at 25° C. hasa specific gravity of 0.98 and a viscosity of 230 cps, and DOW CORNING®1-1405 which is translucent, and at 25° C. has a specific gravity of0.98 and a viscosity of 450 cps.

An imbibing solution is prepared from non-adhesive silicone elastomers,such as, DOW CORNING® 3-1753, 1-1405 and PSA 595 silicone from GeneralElectric, in an appropriate solvent, such as octamethyltrisiloxane(05-20), methyl dimethylformamate (DMF), tetrahydrofuran (THF), mineralspirits, lower alcohols such as C₁ -C₆ alcohols, preferably isopropanol,and ketones solvent from Dow Corning, where the elastomer comprises 10%to 70% by weight of the solution. The elastomer is thoroughly mixed anddissolved in the solvent to form an elastomer solution, by stirring orsimilar mixing techniques. The elastomer solution is placed in a tank orother suitable vessel and the selectively conductive Z-axis material isthen immersed in the elastomer solution to imbibe or impregnate thesolution into the pores of the material. Immersion can be by dipping.Although dipping is one impregnating technique, any other processcapable of impregnating the Z-axis material with the elastomer solution,such as a pressurized spraying, may also be used.

The Z-axis material containing the elastomer solution is placed in adrying rack to air dry for 2 to 15 minutes, preferably 5 to 10 minutes,most preferably 5 minutes. The drying time is controlled by the poresize, material thickness and quantity of solvent. Longer or shorterperiods of air drying may be necessary if thicker Z-axis materials areto be air dried or higher solvent quantities are present. Thereafter,the rack containing the air dried Z-axis impregnated material is placedin a heated oven, maintained at a temperature of between about 95° C.and 145° C., preferably about 120° C., for a period of time between 10and 70 minutes, preferably 30 minutes to remove the solvent. The dryingand heating is carried out until the residual solvent content is reducedto less than about 1.0% by weight, preferably 0.2% by weight.

If on the otherhand the Z-axis material is to be used for the laminatedwafer level contact sheet 9, then the Z-axis material is imbibed with abonding adhesive. The passageways of the Z-axis material can be filledwith an adhesive if the material is to be used as a connector interfacebetween two other conductive materials. Suitable adhesives include epoxyresin, acrylic resin, urethane resin, silicone resin, polyimide resin,cyanate ester resin, or the like. The adhesive is conveniently imbibedinto the pores by immersing the member in a solution of the adhesive.For an epoxy resin, a suitable solvent is methylethylketone. Once theadhesive is imbibed or impregnated into the Z-axis material in order toprovide bonding capability it is baked at 160° C. , which parially curesthe adhesive.

Z-AXIS MATERIALS EXAMPLES

In the following examples, the catalytic treating solution used wasprepared by adding to one liter of D.I. water:

    ______________________________________                                        COMPONENT             AMOUNT (gms)                                            ______________________________________                                        2,6 di-sodium anthraquinone di-sulfonic salt                                                        30                                                        2,7 di-sodium anthraquinone di-sulfonic salt  30                              sorbitol 220 220                                                              cupric acetate 15 15                                                          cupric bromide 0.5 0.5                                                        olin G-10 surfactant 2 2                                                    fluoroboric acid      pH 3.5-3.8                                              ______________________________________                                    

The fixing solution used was 8% sulfuric acid by weight, 92% distilledwater by weight. A stabilizing solution is also used, and contains thefollowing components.

    ______________________________________                                                 STABILIZING SOLUTION                                                 ______________________________________                                                 0.25 g/l palladium chloride                                            8% sulfuric acid by weight                                                    92% distilled water by weight                                               ______________________________________                                    

EXAMPLE 9

As taught in the '467 patent, a stretched porous polytetrafluoroethylenemembrane obtained from W. L. Gore & Associates was treated with awetting agent by immersing it in a solution of 75% methanol, 25% ethanoland of 1 weight % copolymer of tetrafluoroethylene and vinyl alcohol atroom temperature for about 30 seconds.

The wetted membrane was then dipped into the catalytic treating solutionfor 60 seconds and was then dried in an oven at 50° C. for 3 minutes.One surface of the membrane was then masked with dots of a diazo film of6 mil diameters and 6 mil pitch (center to center).

The membrane was then exposed to a collimated UV light source at 1600millijoule for about 2 minutes. After a 5 minute normalization period,the UV treated membrane was then washed for 30 seconds in the fixingsolution to eliminate unexposed catalytic treating solution. Theselectively imaged membrane was then stabilized by dipping into thestabilizing solution for one minute and then washing in distilled waterfor one minute.

The stabilized membrane was then dipped into a copper plating bathcomposition (Shipleys 3) on a per liter of D.I. water basis,

    ______________________________________                                        PLATING SOLUTION                                                              ______________________________________                                        30 grams of ethylenediamine tetra acetic acid                                   6 to 8 grams sodium hydroxide                                                 5 to 7 grams copper II sulfate                                                2 to 3 grams formaldehyde                                                     2 grams of a given surfactant                                               ______________________________________                                    

The membrane was agitated in the bath using an agitation bar for 7 1/2minutes to promote diffusion of copper throughout the pores of themembrane in the catalyzed portion throughout in the Z-axis.

EXAMPLE 10

As taught in the '467 patent, a 6 mil (150 micrometer) thick, stretched,porous polytetrafluoroethylene membrane was wetted by subjecting it to 2propanol by dipping for 1 minute. It was then dipped into the catalytictreating solution for one minute, dried, masked and subjected to UVlight, and then subjected to the fixing and to the stabilizing solutionas in Example 9. The Z-axis material was plated with copper as inExample 9 and coated with copper, as in Example 9.

EXAMPLE 11

A 2 mil thick stretched porous polytetrafluoroethylene membrane wasprepared as in Example 9, except that the masking strips were 3 mil padwith a 10 mil pitch.

EXAMPLES 12-14

The procedure of Example 9 was followed for membranes formed from porouspolyethylene, porous polypropylene and open cell, porous polyurethanesto produce a Z-axis material having irregularly shaped conductivepathways that extend along the Z-axis.

ELASTOMERIC SELECTIVELY CONDUCTIVE Z-AXIS MATERIAL EXAMPLE 15

The Z-axis material of Example 9 was imbibed with the followingsolution:

    ______________________________________                                               ELASTOMER SOLUTION                                                     ______________________________________                                               22 gms of Silicone 3-1765 (Dow Corning)                                  78 gms OS-20 solvent (Dow Corning)                                          ______________________________________                                    

by placing the solution in a tank and dipping the Z-axis material, whichis supported on a frame, into the solution. The impregnated Z-axismaterial was air dried for 5 minutes in a drying rack. The drying rackwas placed in an oven that was heated to 120° C. for 30 minutes toremove solvent.

In Examples 16-20 below, the Z-axis material is impregnated with asilicone elastomer. However, the Z-axis material is also used withoutthe elastomer.

EXAMPLE 16

A membrane formed from a stretched porous polytetrafluoroethylenemembrane having the node-fibril structure shown in FIG. 17(1000×magnification) is 76 μm thick with a density of 0.22 gm/cm³ and anair volume of 70% at 25° C. , and is available from W. L. Gore &Associates, was prepared as in Example 1 to form a Z-axis membrane,except that the masking strips were 2 mil pad with a 5 mil pitch. TheZ-axis membrane was impregnated with a silicone solution containing 20%DOW CORNING® 3-1753 silicone.

EXAMPLE 17

A polytetrafluoroethylene membrane similar to that of Example 16 havingthe node-fibril structure in FIG. 14 (1000×magnification), was preparedas in Example 1 to form a Z-axis membrane, except that the maskingstrips were 8 mils with a 15 mil pitch. The Z-axis membrane wasimpregnated with a silicone solution containing 30% DOW CORNING® 3-1753silicone.

EXAMPLE 18

A stretched porous polytetrafluoroethylene membrane with the node-fibrilstructure shown in FIG. 15 (1500×magnification) that is 40 μm thick,with a density 0.4 gm/cm³ and an air volume of 20% at 25° C. , availablefrom W. L. Gore & Associates, was prepared as in Example 1 to form aZ-axis membrane, except that the masking strips were 8 mils with a 15mil pitch. The Z-axis membrane was impregnated with a silicone solutioncontaining 30% DOW CORNING® 3-1753 silicone.

EXAMPLE 19

A stretched porous polytetrafluoroethylene membrane with the node-fibrilstructure of FIG. 16 (1000×magnification) that is 100 μm thick, with adensity of 0.35 gm/cm³ and an air volume of 70% at 25° C., availablefrom W. L. Gore & Associates, was prepared as in Example 1 to form aZ-axis membrane, except that the masking strips were 8 mils with a pitchof 15 mils. The Z-axis membrane was impregnated with a silicone solutioncontaining 30% DOW CORNING® 3-1753 silicone.

EXAMPLE 20

A stretched porous polytetrafluoroethylene membrane with the node-fibrilstructure of FIG. 17 (1000×magnification) is 150 μm thick, with adensity of 0.20 gm/cm³ and an air volume of 70% at 25° C., and which isavailable from W. L. Gore & Associates, was prepared as in Example 1 toform a Z-axis membrane, except that the masking strips were 8 mils witha 15 mil pitch. The Z-axis membrane was impregnated with a siliconesolution containing 30% DOW CORNING® 3-1765 silicone.

EXAMPLES 21-23

The Z-axis substrate membrane of Examples 9-11 above, are impregnatedwith an epoxy adhesive in order to provide bonding capability and bakedat 160° C.

EXAMPLES 24-29

The Z-axis materials of Examples 15-20 respectively, which form thematrix for the elastomer, are contacted in their unimpregnated statewith an expoxy adhesive resin and heated to 160° C. to form a Z-axisadhesive material.

FIGS. 18 and 19 are scanning electro/micrographs of an 8 mil pad and 8mil pads with a 15 mil pitch respectively.

LAMINATED WAFER LEVEL CONTACT SHEET:

The laminated wafer level contact sheet 9 will be described withreference to FIGS. 20-34 and has an upper surface 8 with contact pads(FIG. 34) arranged in a pattern corresponding to the first terminals 13of the base unit and raised conductive metallic bumps on a lowersurface. Each of the contact pads is electrically coupled to theconductive bumps on the lower surface of the laminated wafer levelcontact sheet 9. When the burn-in device is in use, the conductive bumpsmake contact with the contact pads of the wafer under test.

As seen in FIG. 34, the laminated wafer level contact sheet includesfirst 61 and second layers 62. The first layer 61 is formed from adielectric material 63 with at least one conductive via 64 formed in onesurface 65 respectively coupled to a conductive pad 66 on the othersurface. These layers form the substrate that is processed to form thepart of the wafer level contact sheet. The first layer 61 is a substrate67, preferably GOREFLEX®, available from W. L. Gore and Associates, Inc.Instead of GOREFLEX®, a dielectric material 63, is formed fromSPEEDBOARD C® or an adhesive-filler-ePTFE composite, and clad withcopper.

The second layer 62 is formed from a porous, Z-axis material having aseries of electrically isolated, irregularly shaped conductive, Z-axispathways with a conductive metal bump or contact on a lower surface ofsaid second layer. The conductive bump 67 is coupled to the conductivepads 66 on the first layer 61 through a blind via 64 and the irregularlyshaped, conductive Z-axis pathways in the adhesive containing Z-axismaterial.

As seen in FIGS. 20-34, the laminated wafer level contact sheet of FIG.34 is manufactured from first and second dielectric laminate substrates67 and 68 of FIGS. 20 and 24 respectively. Each dielectric is laminatedwith upper and lower copper layers (FIG. 20).

Substrate 67 includes a conductive layer 69 (such as copper, forexample), a dielectric layer 70 formed from SPEEDBOARD C®k or anadhesive paste ePTFE composite, and a conductive layer 71 (such ascopper, for example). The dielectric layer 70 should not contain amaterial which is resistant to etching by a laser or plasma process,such as a glass reinforced dielectric layer. Suitable dielectricmaterials include, but are not limited to polyimides and polyimidelaminates, epoxy resins, organic materials, or dielectric materialscomprised at least in part of polytetrafluoroethylene. One dielectricmaterial may be obtained from W. L. Gore & Associates, Inc. under thetradename SPEEDBOARD® dielectric material or the adhesive-SiO₂ filledporous substrates described above.

The thickness of the dielectric layer 70 is important. This thicknesswill define the height of the resulting metallic contacts. A photoresistis applied to copper layers 69 and 71, respectively and imaged where awell, e.g., a depression or via is to be formed. Copper in an exposed(imaged) area (not shown) is etched away by any suitable conventionalcopper etchant, such as a cupric chloride based etchant solution. Afterthe copper within the exposed area is etched away a portion ofdielectric layer 70 is visible. The photoresist may then be removed fromthe substrate.

The exposed dielectric portion is ablated away with a laser to define a"well" 72 into which a metallic contact will be formed (FIG. 21). Asshould be understood, the copper layer 69 functions as a mask to permitablation of the exposed dielectric portion 70. The copper layer 71 actsas a stop and will define the bottom of the well 72. The ablation of theexposed dielectric portion may be accomplished by any laser suitable forselective ablation of organic dielectrics, without removing a copperlayer. Lasers which operate in ultra violet wavelengths are particularlywell suited, such as excimer lasers, and frequency tripled or quadrupledYAG lasers. However, other types of lasers are also suitable. The lasermay be operated either in a scanning mode, in which the surface of thesubstrate is swept with a large laser spot, or in a focused beam. Inaddition to laser ablation of the exposed dielectric portion, otherprocesses may be employed to selectively remove the exposed dielectricportion, such as but not limited to plasma etching, reactive ionetching, or chemical etching. However, a laser ablation process isparticularly well suited, as it permits more control over the shape ofthe well. Simple diffraction will provide a tapered conical shape in thecase of scanning mode laser ablation process.

As a result, a blind via 72 is formed. Thereafter the inside of the wellor via 72 is coated with a conductive metal 73, such as copper. Coppermay be deposited by any suitable technique, such as, electrolessplating, sputtering, evaporation, or deposition of a conductive coatingwhich allows direct electrodeposition.

Thereafter, the entire top of the substrate 67, as well as, aprospective pad area 74 is coated with a photoresist 75 (FIG. 22). Theexposed copper 76 on the bottom of substrate 67 is etched away by anysuitable conventional copper etchant, such as a cupric chloride basedetchant solution. The photoresist 75 is then removed from the top andbottom surfaces of the substrate leaving copper pad 77 (FIG. 23).Optionally, a first nickel layer and a second gold layer can bedeposited on the outer surface of pad 77, with the nickel layerfunctioning to reduce diffusion of the gold layer into the copper layer.

The second dielectric laminate substrate 68 (FIG. 24) is identical tosubstrate 67 and includes, an upper copper layer 78, a dielectric 80 anda lower copper layer 79. As with substrate 67, the dielectric layer 80must not comprise a material which is resistant to etching by a laser orplasma process, such as a glass reinforced dielectric layer.

Again, a photoresist is applied to copper layers 78 and 79 (not shown),respectively, and the area where a well, depression or via 81 is to beformed is imaged using conventional techniques. Copper layer 78 in theimaged and exposed area (not shown) is etched away by any suitableconventional copper etchant, such as a cupric chloride based etchantsolution. After the copper within the exposed area is etched, an exposedportion of dielectric layer 80 is visible and ablated away with a laserto define a "well" 81 (FIG. 25). After the well or via 81 has beendefined, the base substrate is processed in any suitable manner whichdeposits a surface conductive layer 82, such as copper, on the sidewalls of the well or via 81 as discuss above with reference to substrate67. Photoresist 83 is then applied to the top of the substrate 68 (FIG.26) and imaged to form pads and/or traces, as well as on the bottom ofsubstrate 68 to avoid plating or metallization.

Areas not protected by the photoresist are metallized with a metal thathas etch selectivity to the copper, such as, nickel and form a nickellayer 84 (FIG. 27). Thereafter, the deposited nickel may be coated witha layer of gold for forming a low resistance contact. The photoresist isthen removed from the upper and lower surfaces of substrate (FIG. 28).

The laminated wafer level contact sheet is then assembled by locating aselectively conductive Z-axis material 87 between said processed firstand second dielectric laminate substrates 85 and 86, with processsubstrate 85 being on top of said Z-axis material 87 (FIG. 29). Thethree layers are laminated together under temperature 435 F and pressure325 psi whereby an adhesive in said Z-axis material 87 bonds substrates85 and 86 thereto.

After the three layer unit 88 is formed (FIG. 30), copper layer 89 isetched away using a copper etching solution discussed above, leavinglayer 90 (FIG. 31). Thereafter, the dielectric 90 is removed leavingcopper layer 91 having a bump 92 (FIG. 32). Photoresist 93 is thenapplied to the via 94 and surrounding areas 96 and 97 on the processedsubstrate (FIG. 33) and copper layer 98 and exposed copper layer 95removed (FIG. 34). The photoresist is removed and the wafer levelcontact sheet is formed. The conductive via 94 is coupled to theconductive pad 99 which is then coupled to the bump 67 through theconductive Z-axis pathways in the Z-axis material 87.

Suitable processes for forming the metal coating on the via include, butare not limited to a conventional electroless copper plating operation,sputtering, evaporation, or deposition of a conductive coating whichallows direct electrodeposition, or any other suitable process.Additional electrolytically deposited copper may be added to thickenthis deposit, thereby providing a more robust surface for additionalprocess steps.

FIG. 35 is a scanning electron micrograph of a bump formed on the waferlevel contact sheet according to the procedure described above.

In FIG. 36, the substrate of FIG. 26 is slightly enlarged to provide thedimensions of the via and pad surface that is formed to provide theconductive bump. As seen in FIG. 36, the via has an upper diameter A,where A is between 25 μm and 75 μm, a bottom diameter B, where B isbetween 10 μm and 60 μm, and a height C, where C is between 20 μm and 75μm. The diameter D of the pad that is formed from photoresist 83, isbetween 35 μm and 150 μm. The bump 67, shown in FIGS. 34 and 37, has asubstantially planar tip 101, having an end diameter of between 5 μm and50 μm, with a tolerance of +/-2 μm, which is temporarily supported bythe via 81.

While preferred embodiments have been shown and described, it will beunderstood that it is not intended to limit the disclosure, but ratherit is intended to cover all modifications within the spirit and scope ofthe invention as defined in the appended claims or their equivalents.

I claim:
 1. A method of forming a base having a high degree of planarity and a low coefficient of thermal expansion for use in providing relablity screening for a semiconductor wafer, said semiconductor wafer having a coefficient of thermal expansion, said method comprising the following steps:providing first and second layers of a metal or metal alloy having a coefficient of thermal expansion that substantially matches the coefficient of thermal expansion of the semiconductor wafer +/-3 parts per million (ppm); machining surfaces of said first and second alloy layers to have a degree of planarity of less than 0.003 inches per linear foot; and laminating said first and second metal or metal alloy layers to one another.
 2. The method according to claim 1, wherein said laminating step includes laminating a layer of copper between said first and second metal or metal alloy layers.
 3. The method according to claim 1, wherein said metal or metal alloy is a nickel alloy which contains between 30 wt. % and 42 wt. % nickel.
 4. The method according to claim 3, wherein said nickel alloy has a coefficient of thermal expansion of between about less than 1 to about 4 ppm/° C.
 5. The method according to claim 2, wherein said laminating step includes laminating a first and a second dielectric layer, each having a T_(g) of a least 200° C., respectively to the copper layer and a respective metal or metal alloy layer.
 6. The method according to claim 5, wherein said dielectric layers are formed from a porous polymer into which an adhesive material is imbibed.
 7. The method according to claim 6, wherein said porous polymer is a porous polyolefin.
 8. The method according to claim 6, wherein said porous polymer is porous polypropylene or porous polyethylene.
 9. The method according to claim 6, wherein said porous polymer is a woven or fibrous material.
 10. The method according to claim 6, wherein said porous polymer is a fluoropolymer.
 11. The method according to claim 6, wherein said porous fluoropolymer includes at least a polytetrafluoroethylene.
 12. The method according to claim 6, wherein said fluoropolymer is an expanded polytetrafluoroethylene.
 13. The method according to claim 2, further including the step of selecting said metal or metal alloy layers to have a combined thickness t₁ and said intermediate copper layer to have a thickness t₂, whereby a ratio t₁ to t₂ is chosen to match the coefficient of thermal expansion of the semiconductor wafer.
 14. The method according to claim 13, wherein each of said metal or metal alloy layers is approximately 115 mils thick.
 15. The method according to claim 6, wherein said first and second dielectric layers each have a T_(g) of at least 200° C.
 16. The method according to claim 13, wherein said thickness ratio provides a coefficient of thermal expansion that matches a wafer formed from silicon, germanium, silicon germanium, silicon carbide, gallium arsenide, selenium or tellurium, +/-3 ppm.
 17. The method according to claim 1, wherein said base has a planarity of approximately 0.001 inches per linear foot.
 18. The method according to claim 5, wherein said dielectric layers are selected based upon their thickness, so that when combined with said metal or metal alloy layers, the base has a coefficient of thermal expansion that matches the coefficient of thermal expansion of the wafer.
 19. The method according to claim 5, wherein each of said dielectric layers is approximately 0.021 inches.
 20. The method according to claim 1, wherein said metal or metal alloy layers each have a dimension of between about 6 inches×6 inches and about 20 inches×20 inches.
 21. The method according to claim 20, wherein said metal or metal alloy layers each have a dimension of approximately 8.0 inches×8.0 inches.
 22. The method according to claim 20, wherein said metal or metal alloy layers each have a dimension of approximately 12.0 inches×12.0 inches.
 23. The method according to claim 20, wherein said metal or metal alloy layers have a dimension of approximately 14.0 inches×14 inches.
 24. The method according to claim 20, wherein said metal or metal alloy sheets have a side dimension between about 4 inches and 24 inches.
 25. The method according to claim 20, wherein said metal or metal alloy sheets have a dimension of approximately 18.0 inches by 18.0 inches.
 26. The method according to claim 20, wherein said metal or metal alloy sheets have a dimension of approximately 20.0 inches by 20.0 inches.
 27. The method according to claim 6, wherein said porous polymer has a void volume of between about 50 and 90%.
 28. The method according to claim 6, wherein said porous polymer is impregnated with an adhesive filler mixture.
 29. The method according to claim 28, wherein said filler comprises between about 25 wt. % and 90 wt. % percent filler.
 30. The method according to claim 28, wherein said filler comprises between about 30 wt % and 70 wt. % of the total weight of said dielectric layers.
 31. The method according to claim 30, where said filler includes non-conductive carbon.
 32. The method according to claim 31, wherein said non-conductive carbon is furnace black.
 33. The method according to claim 30, wherein said filler includes SiO₂ prepared from the vapor combustion of molten silicon.
 34. The method according to claim 33, wherein said filler also includes non-conductive carbon.
 35. The method according to claim 34, wherein said non-conductive carbon is furnace black.
 36. The method according to claim 30, wherein said filler includes TiO₂ or Al₂ O₃ respectively prepared from the vapor combustion of molten titanium and aluminum.
 37. The method according to claim 6, wherein said adhesive is an epoxy resin.
 38. The method according to claim 6, where said adhesive is an acrylic resin.
 39. The method according to claim 6, wherein said adhesive is a urethane resin.
 40. The method according to claim 6, wherein said adhesive is a silicon resin.
 41. The method according to claim 6, wherein said adhesive is a polyimide resin.
 42. The method according to claim 6, wherein said adhesive is a cyanate ester resin.
 43. The method according to claim 6, wherein said adhesive is a mixture of high temperature adhesives. 